US3097963A - Sized glass fibers and composition - Google Patents
Sized glass fibers and composition Download PDFInfo
- Publication number
- US3097963A US3097963A US80260159A US3097963A US 3097963 A US3097963 A US 3097963A US 80260159 A US80260159 A US 80260159A US 3097963 A US3097963 A US 3097963A
- Authority
- US
- United States
- Prior art keywords
- percent
- glass fibers
- weight
- fatty acid
- glass fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003365 glass fiber Substances 0.000 title claims description 123
- 239000000203 mixture Substances 0.000 title description 45
- 239000004744 fabric Substances 0.000 claims description 35
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 25
- 150000004668 long chain fatty acids Chemical group 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 description 44
- 230000004048 modification Effects 0.000 description 37
- 238000012986 modification Methods 0.000 description 37
- 229920001225 polyester resin Polymers 0.000 description 37
- 239000004645 polyester resin Substances 0.000 description 37
- 239000000194 fatty acid Substances 0.000 description 34
- 235000014113 dietary fatty acids Nutrition 0.000 description 31
- 229930195729 fatty acid Natural products 0.000 description 31
- 150000004665 fatty acids Chemical group 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- -1 fatty acid derivative of imidazoline Chemical class 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- 239000000835 fiber Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000005755 formation reaction Methods 0.000 description 15
- 229920000728 polyester Chemical group 0.000 description 15
- 239000007859 condensation product Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000012260 resinous material Substances 0.000 description 12
- 150000005846 sugar alcohols Polymers 0.000 description 12
- QJEBJKXTNSYBGE-UHFFFAOYSA-N 2-(2-heptadecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1CCO QJEBJKXTNSYBGE-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000008117 stearic acid Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000004873 anchoring Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920006305 unsaturated polyester Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- IBTRGWUJQRFLPY-UHFFFAOYSA-N furan-2,5-dione;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.O=C1OC(=O)C=C1 IBTRGWUJQRFLPY-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PVLVQTYSRICFCB-ODZAUARKSA-N (z)-but-2-enedioic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)\C=C/C(O)=O PVLVQTYSRICFCB-ODZAUARKSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000011236 particulate material Substances 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 4
- 239000005050 vinyl trichlorosilane Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229940093430 polyethylene glycol 1500 Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002579 carboxylato group Chemical group [O-]C(*)=O 0.000 description 2
- 229960000359 chromic chloride Drugs 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 2
- 235000007831 chromium(III) chloride Nutrition 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- TWASXFZQHAHVTM-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol oxepane-2,7-dione Chemical compound C(COCCO)O.C1(CCCCC(=O)O1)=O TWASXFZQHAHVTM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KGTZBTUOZOIOBJ-UHFFFAOYSA-N dichloro(ethenyl)silicon Chemical compound Cl[Si](Cl)C=C KGTZBTUOZOIOBJ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- URUGTERYLBWXOS-UHFFFAOYSA-N ethane-1,2-diol;furan-2,5-dione Chemical compound OCCO.O=C1OC(=O)C=C1 URUGTERYLBWXOS-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000009986 fabric formation Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000005076 polymer ester Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31616—Next to polyester [e.g., alkyd]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2402—Coating or impregnation specified as a size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2992—Coated or impregnated glass fiber fabric
Definitions
- This invention relates to glass fibers and strands, yarns and fabrics for-med thereof and a size used on the glass fiber surfaces in strand, yarn and fabric formation, and it relates more particularly to glass fibers and a forming and weaving size applied thereon.
- the application of a size to glass fibers has long be come accepted as a necessary practice to the use of glass fibers in formation of strands and yarns and for weaving or .otherwise processing the glass fibers into various types of woven and non-woven fabrics which may be used as a textile material or as a reinforcement in the manufacture of plastics, laminates, coated fabrics, ropes, screening, and the like.
- the formulation of the size to be employed in combination with the glass fibers has developed into a very extensive and highly technical art in which different types of size compositions have been formulated depending upon the type of application .to be made of the glass fibers and depending also on the materials to be employed in combinations therewith.
- the problems arise from characteristics which are more or less peculiar to glass fibers in that the fibers formed of glass comprise non-porous, rod-like members having perfectly smooth surfaces.
- the principal problems may be divided into three categories:
- the non-porous rod-like elements are subject to complete destruction by mutual abrasion such that the fibers cannot be formed into strands, yarns, fabrics or otherwise processed without some protective agent on the surfaces of the fibers.
- the glass fiber surfaces are hydrophilic in character such that material applied to the surfaces as a coating or as a protective agent are incapable of development of a strong bonding relationship with the glass fiber surfaces and any bond that is developed is soon dissipated by a Water film which forms on the glass fiber surfaces under high humidity conditions.
- the fibers are of a continuous type and are to be formed into strands and plied into yarns for weaving, it is desirable to make use of a size which embodies a film-forming material as a protective agent and which also embodies a lubricant and in which the materials are combined in a manner to provide 'a desirable balance between lubricity and bonding to enable the glass fiber filaments to be held together in strand formation, yet enable sufiicient relative movement between the fibers for processing into strands and yarns and for Weaving the yarns into fabrics.
- the size applied to the continuous glass fibers in strand and yarn formation is unsuitable.
- staple type glass fibers it becomes necessary to make use of a size which not only protect-s the glass fibers and embodies a desirable balance between bonding and lubricity but which also provides some drag so that the sliver formed of the staple glass fibers can be drafted lengthwise through twisters to interfelt and align the fibers without causing a non-uniform ice distribution of fibers through the cross-section of the formed yarn.
- the described forming sizes become unsuitable from the standpoint of the performance characteristics where one depends upon the ability to establish a strong bonding relationship between the coated glass fiber surfaces and the other resinous systems.
- Another object is to provide a new and improved glass fiber system embodying a material on the glass fiber surfaces which is capable, in itself, of use as a glass fiber size and which may be employed in combinations with other ingredients to produce a glass fiber size composition having improved processing and performance characteristics and it is a related object to produce a new and improved forming size for glass fibers.
- the concepts of this invention are embodied in a glass fiber sized, preferably in forming, with a composition containing as an essential ingredient a compound or material which may be defined as a cationic modification of a polyester resin. More specifically, the material may be defined as a reaction product of an unsaturated dibasic acid with a dihydric alcohol to form an unsaturated polyester Which is reacted further with -a fatty acid derivative of imidazoline to produce a cationic-polymeric material having repeating units of fatty acid, imi-dazoline and polyester residues.
- the material which will hereinafter be referred to as the cationic derivative of a polyester resin, is preferably formed by reaction of an unsaturated dibasic acid or anhydride such as maleic acid or anhydride, fumaric acid or anyhydride with a dihydric alcohol such as ethylene glycol, triethylene glycol, diethylene glycol, propylene glycol and the like, to form an unsaturated polyester resin in an intermediate stage of polymeric growth.
- an unsaturated dibasic acid or anhydride such as maleic acid or anhydride, fumaric acid or anyhydride
- a dihydric alcohol such as ethylene glycol, triethylene glycol, diethylene glycol, propylene glycol and the like
- a fatty acid derivative of imidazoline as represented by the reaction product of an imidazoline or other diarnine with a fatty acid such as stearic acid, oleic acid, palmitic "acid, adipic acid, and (the like long chained or short chained fatty acids. It is believed that the reaction between the reaction pro-duct of the imidazoline and fatty acid with the unsaturated polyester occurs through an unreacted hydrogen on the nitrogen of the imidazoline which adds across the unsaturated! group of the dibasic acid to produce the corresponding cationic derivative of a polyester resin.
- the cationic derivative of a polyester resin When the cationic derivative of a polyester resin is formed with a long chained fatty acid, it embodies tack sufficient to bond the glass fibers together in strand and yarn formation without development of excessive fuzzy ends. At the same time, it makes available the drag necessary for drafting a sliver of staple fibers in yarn formation.
- the material also embodies lubricating properties sufficient to enable the fibers to move relative to each other in the processing and in the forming steps.
- the cationic derivative of the polyester resin is capable of the desired film formation to function as a protective agent on the glass fiber surfaces thereby to minimize deterioration of the glass fibers responsive to abrasive forces and also materially to improve the abrasion resistance, hand and feel of the glass fibers and fabrics formed thereof.
- the cationic derivative of the polyester resin when present on the glass fiber surfaces, it appears to render the glass fibers free of static formation. This has been one of the troublesome problems in the processing of glass fibers and fabrics formed thereof, even more so than with the large number of fibers and fabrics formed of other synthetic resinous materials.
- the cationic derivative of a polyester resin is somewhat unlike other heterogeneous combinations of materials previously employed in the formulation of size compositions in that the material embodies groupings, such as the cationic or basic nitrogen groups, which have preferential attraction to groupings that predominate on the glass fiber surfaces so that a type of chemical-physical bond is established therebetween which enables the material to become relatively permanently bonded with the glass fiber surfaces.
- the material is also characterized by excellent compatibility with other resinous materials so that it can be embodied as a component with such other materials to improve the characteristics of other size compositions.
- the unsaturated groupings of the polyester and the basic nitrogen groups of the imidazoline portions of the compound are capable of reaction or orientation with corresponding groupings in resinous materials employed in combinations with the glass fibers to provide a receptive base whereby such resinous materials can become strongly bonded to the heretofore repellent glass fiber surfaces.
- polyester resin wherein the polyester is formed of maleic acid and diethylene glycol and in which the cationic modifier is formed; by the reaction of imidazoline and stearic acid.
- unsaturated dibasic acids and anhydrides and other dihydric alcohols may be used in variable proportions and that the cationic modifier may be formed by the reaction of imidazoline or other dtiamine with other fatty acids ranging from a short chained fatty acid of 3 carbon lengths to a long chained fatty acid of 18 to 24 carbon lengths depending somewhat upon the amount of tackiness, slip and lubricity desired in the final product.
- the unsaturated polyester can also be formed by reacting a saturated acid with an unsaturated alcohol. Butene diol can be reacted with succinic anhydride.
- the latter component is prepared by the reaction of one molecular weight of maleic acid with one molecular weight of diethylene glycol and preferably with a slight excess of diethylene glycol up to about 15-20 percent.
- the reaction is carried out in the presence of a small amount of deactivator, such as hydroquinone, to prevent addition polymerization through the cthylenically unsaturated group of the anhydride and the reaction is carried out by gradually heating the mixture to a temperature of about 220 C. preferably with constant circulation of an inert gas, such as carbon dioxide or nitrogen, through the mixture and reaction kettle for carrying off the water as it is formed and to prevent oxidation of the ingredients.
- Reaction is continued until an acid number of about 25-35 is reached and then the polyester, in an intermediate stage of polymeric growth, is cooled as to a temperature between 3050 F.
- the imidazoline component for modification can be prepared by the reaction of the fatty acid (stearic acid) with diethylene triamine in equimolecular proportions and preferably with a slight excess of the diethyiene triamine. Enough xylene, toluene, or other aromatic solvent is added to eliminate the water produced in the reaction. The reaction is carried out by heating the materials to a temperature of about 180190 C. after which the imidazoline-fatty acid reaction product is cooled to about C. for subsequent admixture with the unsaturated polyester.
- the reaction between the fatty acid imidazoline and the unsaturated polyester is exothermic such that it becomes desirable to extract heat from the mixture to maintain the temperature between -ll0 C. to minimize the amidization of ester groups in the polyester.
- the reaction is continued until the entire product becomes water soluble, usually this will take from 15-20 minutes under the conditions described.
- a suitable cationic modification of a polyester is made available by Quaker Chemical Company of Conshohocken, Pennsylvania, under the designation X1104. The following is representative of the equations involved in the foregoing reactions:
- Substitution may be made of other dibasic acids and anhydrides such as maleic anhydride, fumaric acid or anhydride and the like in equal proportions for the maleic acid.
- Other dihyd-ric alcohols such as ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and the like dihydric alcohols can be substituted for the diethylene glycol in the foregoing preparation in equimolecular amounts.
- Other amines such as ethylene diamine and the like alkyl polyamines can be substituted for the diethylene triamine in forming the imidazoline and fatty acids such as oleic acid,
- . palmitic acid, octanoic acid, adipic acid and the like may be substituted for the stearic acid in the foregoing preparation in substantially equimolecular ratios.
- the fatty acid component is somewhat control-ling with respect to the tackiness, the lubricity and the slip provided by the composition when applied to the glass fiber surfaces. The higher the fatty acid from the standpoint of the chain length, the greater the amount of tackiness, slip and lubricity while decrease in the length of the carbon chain of the fatty acid will tend to provide less tackiness and slip.
- the use of stearic acid as a component in the manufacture of the cationic modification of the polyester resin provides a product which is tacky, which has a high degree of lubricity and gives high slip.
- the stearic acid modification can be used effectively 'as a size for continuous or staple fibers where tack operates to hold the fibers together in yarn formation and to provide a desirable drag in drafting while high slip and lubrication are desirable from a handling standpoint.
- a lower fatty acid such as adipic acid and the like.
- Example 1 1-8 percent by weight of a cationic modification of a polyester resin (X1104, Quaker Chemical Company, Conshohocken, Pennsylvania) 99-92 percent by weight of water
- Example 2 2.0 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline on an equimolecular basis (Quaker X1104) 0.3 percent by weight glass fiber lu'bricant (pelargonate amide solubilized with acetic acid) 97.7 percent by weight water
- Example 3 3.5 percent by weight maleic acid-diethylene glycol condensation product reacted with adipic acid-imidazoline reaction product on an equimolecular basis 0.4 percent by weight of a glass fiber lubricant (pelargonate amide solubilized with acetic acid) 96.1 percent by weight water
- the size composition is applied in the usual manner to the glass fiber surfaces in conjunction with their forming operation.
- the size is applied onto the glass fiber surfaces as the molten streams of glass are attenuated and gathered together to form the strands.
- Application is made by a wiper pad, roller coater or the like in an amount to provide 0.1-0.5 percent ignition loss.
- the size composition can be sprayed onto the fiber surfaces as the fibers are deposited onto a collecting drum or gathered together into a sliver for drafting and twisting.
- Application can also be made after the fibers have been gathered together into the sliver, but before drafting.
- the size is applied in an amount to provide 0.2-1.0 percent ignition loss.
- a size composition which has been found to give excellent results in strand formation to permit Weaving without Warp sizing is characterized by the combination of the cationic derivative of the polyester resin with a polyhydric alcohol polymer ester of a fatty acid.
- the latter comprises the polymer of a polyglycol, such as ethylene glycol, diethylene glycol, propylene glycol, and the like before or after esterification with a fatty acid such as stearic acid, pahnitic acid, oleic acid and the like to form a polyethylene glycol monostearate as an example.
- Example 4 1-6 percent by weight polyhydric alcohol polymer monofatty acid ester 1.5-8 percent by weight cationic modification of a polyester resin (Quaker X1104) 97.5-86 percent by weight water
- Example 5 2.5 percent by weight polyethylene glycol 1500 monostearate 1.5 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline 96 percent by weight water
- Application to the cleaned glass fibers, as provided by the glass fibers in forming or as provided by the glass fibers after the original size has been removed, is made in the manner described in Examples l-3 and application is made in equivalent amounts when measured from the standpoint of ignition loss.
- An important concept of this invention resides in the further combination of glass fibers and a size formulated of the cationic modification of the polyester resin with a particulate material, alone or in combination with a previously described polyhydric alcohol polymer-fatty acid ester.
- the particulate materials function materially to reduce tension and they contribute also to the lubricity and bonding provided by the cationic modification of the polyester resin and combinations thereof with the polyhydric alcohol fatty acid ester.
- the resulting size composition is also characterized by providing improved ha-nd and feel in the strands, yarns and fabrics formed of the glass fibers whereby a substantially universal forming size "7 is provided. For this purpose, use can be made of a small amount of a cellulose pulp, as represented by glassine pulp.
- a size composition it is undesirable to make use of more than percent by Weight of the pulp or other particulate material in the treating composition and the preferred range is an amount less than 2 percent and within the range of 0.1-1 percent.
- the other ingredients can be employed in amounts and in proportions as previously described.
- Example 6 1-6 percent by weight of a polyhydric alcohol polymerfatty acid ester 1-8 percent by weight of a cationic modification of a polyester resin 0.1-1 percent by weight glassine pulp 0.05-0.3 percent by weight glass fiber lubricant 97.85-84.7 percent by Weight water
- Example 7 2.1 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl-imidazoline on an equimolecular basis 5 percent by weight polyethylene emulsion containing by weight of polyethylene resin 0.2 percent by weight of a glass fiber lubricant 92.7 percent by weight water
- Example 8 2.6 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl imidazoline on an equimolecular basis .37 percent by weight polyethylene glycol 20,000 average molecular weight 5.6 percent by weight polyethylene emulsion 25% by weight solids (Bradford Soap and Dye Co.)
- Example 9 2.0 percent by weight polyethylene glycol 400 monopalmitate 2.0 percent by weight adipic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline 0.2 percent by weight glass fiber lubricant (pelargonate amide solubilized with stearic acid) 95.8 percent by weight water
- Example 10 1.5-8.0 percent by weight fumaric acid-polyethylene glycol condensation product reacted with oleyl imidazoline 0.1-0.5 percent by weight cellulose pulp 98.4-91.5 percent by weight water
- Application to clean glass fibers, as previously described, is made by a roller coater, spray coater, or by a wiper pad as the glass fibers are gathered together in strand or yarn formation. Application is made in an amount to pro- "8 vide an ignition loss within the range of 0.1-1.0 percent. Although it is not preferred, the ignition loss can go as high as 2 percent or more.
- a size applied to glass fibers for weaving and for use in combination with epoxy resins :
- Example 11 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 0.3-1.0 percent by weight glycerine 1.0-4.0 percent by weight polyethylene glycol 1500 monostearate 94.4-86 percent by weight water
- Example 12 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydric-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 1.0-4.0 percent by weight polyethylene glycol 1500 monostearate 94.7-87 percent by weight water
- Example 13 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent
- Example 16 The foregoing size compositions operate to protect the glass fiber surfaces in forming and to enhance the bonding relationship between the glass fiber surfaces and resinous materials employed in combinations therewith including the epoxy resins, or other resins formed by condensation reaction between hydroxy or amino groups and other hydroxyl or carboxyl groups.
- the formulation con taining the unsaturated vinyl functions'as an anchoring agent to enhance the bonding relationship between the sized glass fibers and resinous materials formed by addition polymerization through unsaturated ethylenic or acetylenic groups.
- the size compositions of Examples 1l-16 may be formulated to contain other film-forming resinous materials in the combination with the cationic modification of the polyester resin including saturated polyesters, polyvinylpyrrolidones, epoxy resins, polyamides, polyacrylates, and colloids such as gelatin, casein, starches and the like.
- the vinyltrichlorosilane or the gamma-aminopropyl triethoxysilane may be substituted in whole or in part with other unsaturated organo silicon compounds or other unsaturated Werner complex compounds or such organo silicon compounds or Werner complex compounds containing an active amine nitrogen.
- the lubricant such as the Hoffman RL-l85A, which is a pelargonate amide sol-ubilized with acetic acid, may be substituted with other glass fiber lubricating materials such as tetraethylenepentamine-stearic acid condensate solubilized with acetic acid, hydrogenated vegetable oils or the like.
- the cationic modification of the polyester resin is extremely beneficial in protecting the glass fibers from breakage such that it could easily function as a single component forming size for all applications, especially if means are embodied to minimize some of the tension problems. Any tension can be alleviated, if not entirely overcome, by a suitable modification of the cationic modification of the polyester by variation of the straight chain of the fatty acid either to a shorter length or else to make use of a carboxylic acid, as represented by polyacrylic acid or a dirnerized acid.
- the forming size of the cationic modification of the polyester resin would comprise a suitable base for the application of polyethylene Waxes to the filaments since the stearic or other fatty acid groups present in the composition are capable of reaction with the polyethylene to enable complete compatibility. This would operate markedly to increase the wet-out characteristics for the manufacture of polyethylene coated glass fiber yarns.
- Sizes formulated of the cationic modification of the polyester resin are capable of complete removal by burning out without flame in the coronizing process wherein the glass fibers are heated to a temperature within the range of 11001300 F., in an oxidizing atmosphere, for size removal to weave set and relax the glass fibers.
- the heat treating process is now identified by the Owens-Corning Fiberglas Corporation as the coronizing process.
- the size composition could be formulated to contain a coupling agent which would be left on the glass fiber surfaces after heat treatment to remove the other components of the size composition. This would result in a glass fiber, yarn or fabric with a fixed coupling agent on the surface.
- the coupling agent use can be made of the unsaturated organo silicon compounds such as vinyltrichlorosilane, vinyltriethoxysilane, vinyldichlorosilane or the compound identified as gamma-aminopropyl triethoxysilane.
- Use could be made of an unsaturated Werner complex compound such as methacrylato chromic chloride and the like.
- the following are further examples of treating compositions embodying the features of this invention and which contain an anchoring agent of the type described.
- Example 17 1-8 percent by weight of a cationic modification of a 14) polyester resin (X1104, Quaker Chemical Company) 1 percent by weight vinyltrichlorosilane Remainder water
- Example 18 2.0 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline on an equimolecular basis (Quaker X1104) 0.3 percent by weight glass fiber lubricant (pelargonate amide solubilized with acetic acid) 1.0 percent by weight methacrylato chromic chloride 96.7 percent by weight water
- Example 19 2.1 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl imidazoline on an equimolecular basis 5.0 percent by weight polyethylene emulsion containing 25% by weight of polyethylene resin 0.2 percent by weight of a glass fiber lubricant 1.5 percent by weight gamma-aminopropyl triethoxysil-ane 91.2 percent by weight water
- Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces having, as an essential ingredient, the neaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- the unsaturated polyester resin former comprises the condensation reaction product of a dihydric alcohol and a compound selected from the group consisting of an unsaturated dibasic acid and an unsaturated dibasic acid anhydride.
- polyester comprises the reaction product of one molecular weight of a dihydric alcohol to l1.15 molecular weights of a dibasic acid.
- Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces comprising the combination of a polyhydric alcohol polymer of a fatty acid and the product of the reaction of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- the particulate component comprises a synthetic resinous material dispersed as fine particles in an aqueous medium and in which the synthetic resinous polymer is selected from the group consisting of polytetrafluoroethylene, polyethylene, polyvinyl acetate and polyvinylidene chloride.
- Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces comprising an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an :ethylenically unsaturated group, and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester rresin former in an uncured stage.
- an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an :ethylenically unsaturated group
- the method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing, as an essential ingredient, a cationic modification of a polyester resin comprising the product of the reaction of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- the method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing a polyhydric alcohol polymer mono-fatty acid ester and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- the method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing a dispersed component selected from the group consisting of a cellulose pulp and finely divided synthetic organic resinous polymer and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- a size composition containing a dispersed component selected from the group consisting of a cellulose pulp and finely divided synthetic organic resinous polymer and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- the method of treating glass fibers comprising sizing the glass fibers with an aqueous composition containing an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached directly to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an unsaturated ethylenic group and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
- an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached directly to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an unsaturated ethylenic group and a cationic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyamides (AREA)
Description
United States Patent 3,097,63 SIZED GLASS FIBERS AND COMPOSITION Remus F. Caroselli and Alfred Marzocchi, Cumberland,
R.I., assignors to Owens-Corning Fiberglas Corporation, a corporation of Delaware N0 Drawing. Filed Mar. 30, 1959, Ser. No. 802,601 21 Claims. (Cl. 117-126) This invention relates to glass fibers and strands, yarns and fabrics for-med thereof and a size used on the glass fiber surfaces in strand, yarn and fabric formation, and it relates more particularly to glass fibers and a forming and weaving size applied thereon.
The application of a size to glass fibers has long be come accepted as a necessary practice to the use of glass fibers in formation of strands and yarns and for weaving or .otherwise processing the glass fibers into various types of woven and non-woven fabrics which may be used as a textile material or as a reinforcement in the manufacture of plastics, laminates, coated fabrics, ropes, screening, and the like. The formulation of the size to be employed in combination with the glass fibers has developed into a very extensive and highly technical art in which different types of size compositions have been formulated depending upon the type of application .to be made of the glass fibers and depending also on the materials to be employed in combinations therewith.
In brief, the problems arise from characteristics which are more or less peculiar to glass fibers in that the fibers formed of glass comprise non-porous, rod-like members having perfectly smooth surfaces. The principal problems may be divided into three categories:
(1) No natural bond exists between the perfectly smooth surfaces of the glass fibers which is comparable to the bonding relationship capable of being developed by the large number of fibrils extending outwardly from the surfaces of the natural Wool or cotton fibers. As a result, the glass fibers tend to slip relative to each other and no bonding relationship naturally develops therebetween.
(2) The non-porous rod-like elements are subject to complete destruction by mutual abrasion such that the fibers cannot be formed into strands, yarns, fabrics or otherwise processed without some protective agent on the surfaces of the fibers.
(3) The glass fiber surfaces are hydrophilic in character such that material applied to the surfaces as a coating or as a protective agent are incapable of development of a strong bonding relationship with the glass fiber surfaces and any bond that is developed is soon dissipated by a Water film which forms on the glass fiber surfaces under high humidity conditions.
Thus, if the fibers are of a continuous type and are to be formed into strands and plied into yarns for weaving, it is desirable to make use of a size which embodies a film-forming material as a protective agent and which also embodies a lubricant and in which the materials are combined in a manner to provide 'a desirable balance between lubricity and bonding to enable the glass fiber filaments to be held together in strand formation, yet enable sufiicient relative movement between the fibers for processing into strands and yarns and for Weaving the yarns into fabrics.
If the glass fibers are of the staple type, the size applied to the continuous glass fibers in strand and yarn formation is unsuitable. With staple type glass fibers it becomes necessary to make use of a size which not only protect-s the glass fibers and embodies a desirable balance between bonding and lubricity but which also provides some drag so that the sliver formed of the staple glass fibers can be drafted lengthwise through twisters to interfelt and align the fibers without causing a non-uniform ice distribution of fibers through the cross-section of the formed yarn.
When the glass fibers in strand, yarn orfabric forma tion are to be employed in combinations with other resinous materials in finishing the fabric or as a reinforcement in the manufacture of plastics, laminates or coated fabrics, the described forming sizes become unsuitable from the standpoint of the performance characteristics where one depends upon the ability to establish a strong bonding relationship between the coated glass fiber surfaces and the other resinous systems. Thus it becomes necessary either .to remove the size previously applied to the glass fiber surface-s and modify the glass fiber surfaces by the application of an anchoring agent or else it becomes necessary specifically to formulate the size composition to provide the desired processing and performance characteristics by the use of a particular resinous system, depending upon the type of resinous material to be employed in combinations with the glass fibers or else to make use of a particular resinous system in combination with an anchoring agent.
The foregoing is representative of many years of extensive research and development which has been devoted to the subject and it forms the subject matter of many hundreds of patents on glass fiber finishing and size compositions and other glass fiber treating materials.
It will be obvious that one of the major objectives of research and development in the field of glass fibers is aimed towards the formulation of a universal size which can be applied to glass fibers to provide the desired processing and performance characteristics and it is an object of this invention to produce a universal size of the type described.
Another object is to provide a new and improved glass fiber system embodying a material on the glass fiber surfaces which is capable, in itself, of use as a glass fiber size and which may be employed in combinations with other ingredients to produce a glass fiber size composition having improved processing and performance characteristics and it is a related object to produce a new and improved forming size for glass fibers.
The concepts of this invention are embodied in a glass fiber sized, preferably in forming, with a composition containing as an essential ingredient a compound or material which may be defined as a cationic modification of a polyester resin. More specifically, the material may be defined as a reaction product of an unsaturated dibasic acid with a dihydric alcohol to form an unsaturated polyester Which is reacted further with -a fatty acid derivative of imidazoline to produce a cationic-polymeric material having repeating units of fatty acid, imi-dazoline and polyester residues.
The material, which will hereinafter be referred to as the cationic derivative of a polyester resin, is preferably formed by reaction of an unsaturated dibasic acid or anhydride such as maleic acid or anhydride, fumaric acid or anyhydride with a dihydric alcohol such as ethylene glycol, triethylene glycol, diethylene glycol, propylene glycol and the like, to form an unsaturated polyester resin in an intermediate stage of polymeric growth. The latter is then reacted with a fatty acid derivative of imidazoline as represented by the reaction product of an imidazoline or other diarnine with a fatty acid such as stearic acid, oleic acid, palmitic "acid, adipic acid, and (the like long chained or short chained fatty acids. It is believed that the reaction between the reaction pro-duct of the imidazoline and fatty acid with the unsaturated polyester occurs through an unreacted hydrogen on the nitrogen of the imidazoline which adds across the unsaturated! group of the dibasic acid to produce the corresponding cationic derivative of a polyester resin.
When the cationic derivative of a polyester resin is formed with a long chained fatty acid, it embodies tack sufficient to bond the glass fibers together in strand and yarn formation without development of excessive fuzzy ends. At the same time, it makes available the drag necessary for drafting a sliver of staple fibers in yarn formation. The material also embodies lubricating properties sufficient to enable the fibers to move relative to each other in the processing and in the forming steps.
The cationic derivative of the polyester resin is capable of the desired film formation to function as a protective agent on the glass fiber surfaces thereby to minimize deterioration of the glass fibers responsive to abrasive forces and also materially to improve the abrasion resistance, hand and feel of the glass fibers and fabrics formed thereof. In addition to the aforementioned combination of characteristics desired to be developed in a universal forming or finishing size, when the cationic derivative of the polyester resin is present on the glass fiber surfaces, it appears to render the glass fibers free of static formation. This has been one of the troublesome problems in the processing of glass fibers and fabrics formed thereof, even more so than with the large number of fibers and fabrics formed of other synthetic resinous materials.
The cationic derivative of a polyester resin is somewhat unlike other heterogeneous combinations of materials previously employed in the formulation of size compositions in that the material embodies groupings, such as the cationic or basic nitrogen groups, which have preferential attraction to groupings that predominate on the glass fiber surfaces so that a type of chemical-physical bond is established therebetween which enables the material to become relatively permanently bonded with the glass fiber surfaces. The material is also characterized by excellent compatibility with other resinous materials so that it can be embodied as a component with such other materials to improve the characteristics of other size compositions. It is capable also of functioning as an anchoring agent on the glass fiber surfaces to tie in other resinous materials employed in combinations with the glass fibers in the manufacture of glass fiber reinforced plastics, laminates, coated fabrics, cord and the like, or in providing a receptive base on the glass fiber surfaces for dyestuffs, varnishes, or other printing or coloring compositions employed in the manufacture of dyed or printed glass fiber fabrics. The unsaturated groupings of the polyester and the basic nitrogen groups of the imidazoline portions of the compound are capable of reaction or orientation with corresponding groupings in resinous materials employed in combinations with the glass fibers to provide a receptive base whereby such resinous materials can become strongly bonded to the heretofore repellent glass fiber surfaces.
Thus it appears that we have taken a major step toward the formulation of a universal size for use in the treatment of glass fibers in forming; which can :be used to advantage either in the sizing of continuous glass fibers in strand formation or discontinuous glass fibers in yarn formation; which can be used as an anchoring agent to improve the bonding relationship of various materials with glass fiber surfaces; which can be applied to the glass fiber surfaces subsequent to forming as a protection or anchoring agent, and which need not be removed from the glass fiber surfaces when the glass fibers or fabrics formed (thereof are to be employed as a reinforcement in the manufacture of glass fiber reinforced plastics, laminates, coated fabrics and other glass fiber reinforced or filled structures.
Referring .to the manufacture of the cationic modification of the polyester resin, illustration will be made of a cationic modification of a polyester resin wherein the polyester is formed of maleic acid and diethylene glycol and in which the cationic modifier is formed; by the reaction of imidazoline and stearic acid. It will be understood that other unsaturated dibasic acids and anhydrides and other dihydric alcohols may be used in variable proportions and that the cationic modifier may be formed by the reaction of imidazoline or other dtiamine with other fatty acids ranging from a short chained fatty acid of 3 carbon lengths to a long chained fatty acid of 18 to 24 carbon lengths depending somewhat upon the amount of tackiness, slip and lubricity desired in the final product. The unsaturated polyester can also be formed by reacting a saturated acid with an unsaturated alcohol. Butene diol can be reacted with succinic anhydride.
In the preparation of the cationic modification of the polyester resin, the latter component is prepared by the reaction of one molecular weight of maleic acid with one molecular weight of diethylene glycol and preferably with a slight excess of diethylene glycol up to about 15-20 percent. The reaction is carried out in the presence of a small amount of deactivator, such as hydroquinone, to prevent addition polymerization through the cthylenically unsaturated group of the anhydride and the reaction is carried out by gradually heating the mixture to a temperature of about 220 C. preferably with constant circulation of an inert gas, such as carbon dioxide or nitrogen, through the mixture and reaction kettle for carrying off the water as it is formed and to prevent oxidation of the ingredients. Reaction is continued until an acid number of about 25-35 is reached and then the polyester, in an intermediate stage of polymeric growth, is cooled as to a temperature between 3050 F.
The imidazoline component for modification can be prepared by the reaction of the fatty acid (stearic acid) with diethylene triamine in equimolecular proportions and preferably with a slight excess of the diethyiene triamine. Enough xylene, toluene, or other aromatic solvent is added to eliminate the water produced in the reaction. The reaction is carried out by heating the materials to a temperature of about 180190 C. after which the imidazoline-fatty acid reaction product is cooled to about C. for subsequent admixture with the unsaturated polyester.
The reaction between the fatty acid imidazoline and the unsaturated polyester is exothermic such that it becomes desirable to extract heat from the mixture to maintain the temperature between -ll0 C. to minimize the amidization of ester groups in the polyester. The reaction is continued until the entire product becomes water soluble, usually this will take from 15-20 minutes under the conditions described. A suitable cationic modification of a polyester is made available by Quaker Chemical Company of Conshohocken, Pennsylvania, under the designation X1104. The following is representative of the equations involved in the foregoing reactions:
In general, it is desirable to calculate for a ratio of polyester to imidazoline on the basis of one molecular weight of imidazoline per mol of dibasic acid in the polymer or per unsaturated group in the polyester. In actual practice, this amounts to 80-90 percent by weight imidazoline per double bond.
Substitution may be made of other dibasic acids and anhydrides such as maleic anhydride, fumaric acid or anhydride and the like in equal proportions for the maleic acid. Other dihyd-ric alcohols such as ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and the like dihydric alcohols can be substituted for the diethylene glycol in the foregoing preparation in equimolecular amounts. Other amines such as ethylene diamine and the like alkyl polyamines can be substituted for the diethylene triamine in forming the imidazoline and fatty acids such as oleic acid,
. palmitic acid, octanoic acid, adipic acid and the like may be substituted for the stearic acid in the foregoing preparation in substantially equimolecular ratios. The fatty acid component is somewhat control-ling with respect to the tackiness, the lubricity and the slip provided by the composition when applied to the glass fiber surfaces. The higher the fatty acid from the standpoint of the chain length, the greater the amount of tackiness, slip and lubricity while decrease in the length of the carbon chain of the fatty acid will tend to provide less tackiness and slip. For example, the use of stearic acid as a component in the manufacture of the cationic modification of the polyester resin provides a product which is tacky, which has a high degree of lubricity and gives high slip. Thus the stearic acid modification can be used effectively 'as a size for continuous or staple fibers where tack operates to hold the fibers together in yarn formation and to provide a desirable drag in drafting while high slip and lubrication are desirable from a handling standpoint.
When less slip and less tackiness are desired, use can be made of a lower fatty acid such as adipic acid and the like.
The following are representative of forming sizes embodying the cationic modification of a polyester resin as essential components thereof:
Example 1 1-8 percent by weight of a cationic modification of a polyester resin (X1104, Quaker Chemical Company, Conshohocken, Pennsylvania) 99-92 percent by weight of water Example 2 2.0 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline on an equimolecular basis (Quaker X1104) 0.3 percent by weight glass fiber lu'bricant (pelargonate amide solubilized with acetic acid) 97.7 percent by weight water Example 3 3.5 percent by weight maleic acid-diethylene glycol condensation product reacted with adipic acid-imidazoline reaction product on an equimolecular basis 0.4 percent by weight of a glass fiber lubricant (pelargonate amide solubilized with acetic acid) 96.1 percent by weight water The size composition is applied in the usual manner to the glass fiber surfaces in conjunction with their forming operation. In the forming of continuous textile fibers of glass, the size is applied onto the glass fiber surfaces as the molten streams of glass are attenuated and gathered together to form the strands. Application is made by a wiper pad, roller coater or the like in an amount to provide 0.1-0.5 percent ignition loss.
In the formation of yarns of discontinuous or staple fibers, the size composition can be sprayed onto the fiber surfaces as the fibers are deposited onto a collecting drum or gathered together into a sliver for drafting and twisting.
Application can also be made after the fibers have been gathered together into the sliver, but before drafting. In the yarn, the size is applied in an amount to provide 0.2-1.0 percent ignition loss.
A size composition which has been found to give excellent results in strand formation to permit Weaving without Warp sizing is characterized by the combination of the cationic derivative of the polyester resin with a polyhydric alcohol polymer ester of a fatty acid. The latter comprises the polymer of a polyglycol, such as ethylene glycol, diethylene glycol, propylene glycol, and the like before or after esterification with a fatty acid such as stearic acid, pahnitic acid, oleic acid and the like to form a polyethylene glycol monostearate as an example. I he latter appears to contribute to the lubricity and bonding of the glass fiber filaments in the strand, yarn or fabric without interfering with the desirable characteristics of the cationic derivative of the polyester resin. In fact, the poly- =glycol ester appears to function in combination with the cationic derivative of the polyester to enhance the functional and performance characteristics thereof as a size or finish on the glass fiber surfaces. It is desirable to provide a soft bond which allows the yarn to bend without filament separation.
In the foregoing modification, it is desirable to make use of a polyhydric alcohol polymer having a molecular Weight greater than 200 but less than 2000. It will be understood that lower polymers can be used including the polyhydric alcohol.
The following are representative of size compositions embodying the aforementioned modification of this invention:
Example 4 1-6 percent by weight polyhydric alcohol polymer monofatty acid ester 1.5-8 percent by weight cationic modification of a polyester resin (Quaker X1104) 97.5-86 percent by weight water Example 5 2.5 percent by weight polyethylene glycol 1500 monostearate 1.5 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline 96 percent by weight water Application to the cleaned glass fibers, as provided by the glass fibers in forming or as provided by the glass fibers after the original size has been removed, is made in the manner described in Examples l-3 and application is made in equivalent amounts when measured from the standpoint of ignition loss.
An important concept of this invention resides in the further combination of glass fibers and a size formulated of the cationic modification of the polyester resin with a particulate material, alone or in combination with a previously described polyhydric alcohol polymer-fatty acid ester. The particulate materials function materially to reduce tension and they contribute also to the lubricity and bonding provided by the cationic modification of the polyester resin and combinations thereof with the polyhydric alcohol fatty acid ester. The resulting size composition is also characterized by providing improved ha-nd and feel in the strands, yarns and fabrics formed of the glass fibers whereby a substantially universal forming size "7 is provided. For this purpose, use can be made of a small amount of a cellulose pulp, as represented by glassine pulp. While not equivalent to cellulose pulp, desirable results are also secured by the use of other particulated materials in the form of organic resinous polymers introduced as suspensions or emulsions such as a suspension of polytetrafluoroethylene, an emulsion of polyethylene, an emulsion of polyvinyl acetate or polyvinylidene chloride and the like. These materials form particles in the coating as distinguished from a continuous film to break up the smoothness and continuity and to provide islands or hearing points for flexure of the coating. The use of these materials in the described size compositions results in a marked decrease in drag of glass yarns as represented by a reduction in tension from 80 grams to 30 grams when comparing a size composition formulated with or without the particulate component with the cationic modification of a polyester resin size.
In a size composition, it is undesirable to make use of more than percent by Weight of the pulp or other particulate material in the treating composition and the preferred range is an amount less than 2 percent and within the range of 0.1-1 percent. The other ingredients can be employed in amounts and in proportions as previously described.
The following are examples of size compositions embodying the described concepts:
Example 6 1-6 percent by weight of a polyhydric alcohol polymerfatty acid ester 1-8 percent by weight of a cationic modification of a polyester resin 0.1-1 percent by weight glassine pulp 0.05-0.3 percent by weight glass fiber lubricant 97.85-84.7 percent by Weight water Example 7 2.1 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl-imidazoline on an equimolecular basis 5 percent by weight polyethylene emulsion containing by weight of polyethylene resin 0.2 percent by weight of a glass fiber lubricant 92.7 percent by weight water Example 8 2.6 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl imidazoline on an equimolecular basis .37 percent by weight polyethylene glycol 20,000 average molecular weight 5.6 percent by weight polyethylene emulsion 25% by weight solids (Bradford Soap and Dye Co.)
0.1 percent by weight glass fiber lubricant 91.33 percent by weight water Example 9 2.0 percent by weight polyethylene glycol 400 monopalmitate 2.0 percent by weight adipic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline 0.2 percent by weight glass fiber lubricant (pelargonate amide solubilized with stearic acid) 95.8 percent by weight water Example 10 1.5-8.0 percent by weight fumaric acid-polyethylene glycol condensation product reacted with oleyl imidazoline 0.1-0.5 percent by weight cellulose pulp 98.4-91.5 percent by weight water Application to clean glass fibers, as previously described, is made by a roller coater, spray coater, or by a wiper pad as the glass fibers are gathered together in strand or yarn formation. Application is made in an amount to pro- "8 vide an ignition loss within the range of 0.1-1.0 percent. Although it is not preferred, the ignition loss can go as high as 2 percent or more.
The following will represent other specific formulations embodying the cationic modification of a polyester resin as an essential component in combination with other ingredients incorporated for various purposes in the size composition.
A size applied to glass fibers for weaving and for use in combination with epoxy resins:
Example 11 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 0.3-1.0 percent by weight glycerine 1.0-4.0 percent by weight polyethylene glycol 1500 monostearate 94.4-86 percent by weight water Example 12 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydric-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 1.0-4.0 percent by weight polyethylene glycol 1500 monostearate 94.7-87 percent by weight water Example 13 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 0.3-1.0 percent by weight glycerine 95 .4-90 percent by Weight water Example 14 4.0-8.0 percent by weight cationic modification of a polyester resin (maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline) 0.3-1.0 percent by weight gamma-aminopropyl triethoxysilane 95.7-91 percent by weight Water Example 15 4.0 percent by weight cationic modification of an unsaturated polyester (maleic anhydride-ethylene glycol condensation product reacted with a fatty acid modified imidazoline) 0.3 percent by weight vinyltrichlorosilane 0.3 percent by weight glycerine 2.0 percent by weight ethylene glycol 600 mono-stearate 93.4 percent by weight water.
Example 16 The foregoing size compositions operate to protect the glass fiber surfaces in forming and to enhance the bonding relationship between the glass fiber surfaces and resinous materials employed in combinations therewith including the epoxy resins, or other resins formed by condensation reaction between hydroxy or amino groups and other hydroxyl or carboxyl groups. The formulation con taining the unsaturated vinyl functions'as an anchoring agent to enhance the bonding relationship between the sized glass fibers and resinous materials formed by addition polymerization through unsaturated ethylenic or acetylenic groups.
The size compositions of Examples 1l-16 may be formulated to contain other film-forming resinous materials in the combination with the cationic modification of the polyester resin including saturated polyesters, polyvinylpyrrolidones, epoxy resins, polyamides, polyacrylates, and colloids such as gelatin, casein, starches and the like.
As the coupling agents, the vinyltrichlorosilane or the gamma-aminopropyl triethoxysilane may be substituted in whole or in part with other unsaturated organo silicon compounds or other unsaturated Werner complex compounds or such organo silicon compounds or Werner complex compounds containing an active amine nitrogen. The lubricant such as the Hoffman RL-l85A, which is a pelargonate amide sol-ubilized with acetic acid, may be substituted with other glass fiber lubricating materials such as tetraethylenepentamine-stearic acid condensate solubilized with acetic acid, hydrogenated vegetable oils or the like.
We have found that the cationic modification of the polyester resin is extremely beneficial in protecting the glass fibers from breakage such that it could easily function as a single component forming size for all applications, especially if means are embodied to minimize some of the tension problems. Any tension can be alleviated, if not entirely overcome, by a suitable modification of the cationic modification of the polyester by variation of the straight chain of the fatty acid either to a shorter length or else to make use of a carboxylic acid, as represented by polyacrylic acid or a dirnerized acid.
It has been found that the forming size of the cationic modification of the polyester resin would comprise a suitable base for the application of polyethylene Waxes to the filaments since the stearic or other fatty acid groups present in the composition are capable of reaction with the polyethylene to enable complete compatibility. This would operate markedly to increase the wet-out characteristics for the manufacture of polyethylene coated glass fiber yarns.
Sizes formulated of the cationic modification of the polyester resin are capable of complete removal by burning out without flame in the coronizing process wherein the glass fibers are heated to a temperature within the range of 11001300 F., in an oxidizing atmosphere, for size removal to weave set and relax the glass fibers. The heat treating process is now identified by the Owens-Corning Fiberglas Corporation as the coronizing process. Thus the size composition could be formulated to contain a coupling agent which would be left on the glass fiber surfaces after heat treatment to remove the other components of the size composition. This would result in a glass fiber, yarn or fabric with a fixed coupling agent on the surface. As the coupling agent, use can be made of the unsaturated organo silicon compounds such as vinyltrichlorosilane, vinyltriethoxysilane, vinyldichlorosilane or the compound identified as gamma-aminopropyl triethoxysilane. Use could be made of an unsaturated Werner complex compound such as methacrylato chromic chloride and the like. The following are further examples of treating compositions embodying the features of this invention and which contain an anchoring agent of the type described.
Example 17 1-8 percent by weight of a cationic modification of a 14) polyester resin (X1104, Quaker Chemical Company) 1 percent by weight vinyltrichlorosilane Remainder water Example 18 2.0 percent by weight maleic anhydride-diethylene glycol condensation product reacted with stearyl imidazoline on an equimolecular basis (Quaker X1104) 0.3 percent by weight glass fiber lubricant (pelargonate amide solubilized with acetic acid) 1.0 percent by weight methacrylato chromic chloride 96.7 percent by weight water Example 19 2.1 percent by weight maleic acid-diethylene glycol condensation product modified with stearyl imidazoline on an equimolecular basis 5.0 percent by weight polyethylene emulsion containing 25% by weight of polyethylene resin 0.2 percent by weight of a glass fiber lubricant 1.5 percent by weight gamma-aminopropyl triethoxysil-ane 91.2 percent by weight water It will be apparent from the foregoing that we have provided a number of new and improved treating compositions for glass fibers which can be applied to the glass fibers in forming as a substantially universal size to improve the processing and the performance characteristics of the glass fibers in strand and yarn formation and in the fabrication of fabric thereof to be used as a textile material or in combinations with resinous materials in the manufacture of reinforced plastics, laminates, coated fabrics, cords, and the like composite structures.
It will be understood that numerous changes may be made in the formulation of the materials and in their application onto the glass fiber surfaces without departing from the spirit of the invention, especially as defined in the following claims.
We claim:
1. Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces having, as an essential ingredient, the neaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
2. Glass fibers and fabrics as claimed in claim 1 in which the unsaturated polyester resin former comprises the condensation reaction product of a dihydric alcohol and a compound selected from the group consisting of an unsaturated dibasic acid and an unsaturated dibasic acid anhydride.
3. Glass fibers and fabrics as claimed in claim 1 in which the imidazoline derivative is formed by the reaction of an alkyl polyamine and adipic acid.
4. Glass fibers and fabrics as claimed in claim 1 in which the imidazoline derivative is formed by the reaction of an alkyl polyamine with polyacrylic acid.
5. Glass fibers and fabrics as claimed in claim 1 in which the polyester comprises the reaction product of one molecular weight of a dihydric alcohol to l1.15 molecular weights of a dibasic acid.
6. Glass fibers and fabrics as claimed in claim 1 in which the imidazoline has a long chain fatty acid and is formed by reaction of an alkyl polyamine and along chain fatty acid of more than 12 carbon atoms.
7. Glass fibers and fabrics as claimed in claim 6 in which the fatty acid reacted with the alkyl polyamine comprises stearic acid.
8. Glass fibers and fabrics as claimed in claim 6 in which the fatty acid reacted with the alkyl polyamine comprises a dimerized fatty acid.
9. Glass fibers and fabrics as claimed in claim 6 in which the alkyl polyamine is selected from the group con sisting of ethylene diamine and diethylene triamine.
10. Glass fibers and fabrics as claimed in claim 6 in 1 1 which the alkyl polyamine and fatty acid are reacted in the ratio of one molecular weight of alkyl polyamine to 1-1.15 mols of the fatty acid.
11. Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces comprising the combination of a polyhydric alcohol polymer of a fatty acid and the product of the reaction of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
12. Glass fibers and fabrics as claimed in claim 11 in which the polyhydric alcohol polymer of a fatty acid and the reaction product of the polyester and imidazoline are present in the ratio of 1-6 parts by weight of the polyhydric alcohol polymer to 1.5-8 parts by weight of the reaction product of the polyester and the imidazoline.
13. Glass fibers and fabrics as claimed in claim 11 in which the polyhydric alcohol polymer of which the fatty acid is formed has a molecular weight greater than 200 but less than 2000.
. cationic modification :of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
15. Glass fibers and fabrics as claimed in claim 14 in which the particulate component comprises a synthetic resinous material dispersed as fine particles in an aqueous medium and in which the synthetic resinous polymer is selected from the group consisting of polytetrafluoroethylene, polyethylene, polyvinyl acetate and polyvinylidene chloride.
16. Glass fibers and fabrics as claimed in claim 15 in which the particulate material is present in the size composition in an amount less than 5 percent by weight but more than 0.1 percent by weight and in which the cationic modification of the polyester resin former is present in an amount within the range of 1-8 percent by weight of the composition.
17. Glass fibers and fabrics formed thereof and a size on the glass fiber surfaces comprising an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an :ethylenically unsaturated group, and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester rresin former in an uncured stage.
18. The method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing, as an essential ingredient, a cationic modification of a polyester resin comprising the product of the reaction of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
19. The method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing a polyhydric alcohol polymer mono-fatty acid ester and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
20. The method of treating glass fibers comprising coating the glass fibers in forming with a size composition containing a dispersed component selected from the group consisting of a cellulose pulp and finely divided synthetic organic resinous polymer and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
21. The method of treating glass fibers comprising sizing the glass fibers with an aqueous composition containing an anchoring agent selected from the group consisting of an organo silicon compound in which an organic group attached directly to the silicon atom contains an unsaturated ethylenic group and a Werner complex compound in which the carboxylato group coordinated with the trivalent nuclear chromium atom contains an unsaturated ethylenic group and a cationic modification of a polyester resin comprising the reaction product of an imidazoline having a long chain fatty acid group in which the long chain fatty acid group contains at least 5 carbon atoms and an unsaturated polyester resin former in an uncured stage.
References Cited in the file of this patent UNITED STATES PATENTS 2,146,210 Graves Feb. 7, 1939 2,468,086 Latham et al Apr. 26, 1949 2,544,668 Goebel et al Mar. 13, 1951 2,552,910 Steinman May 15, 1951 2,563,288 Steinman Aug. 7, 1951 2,563,289 Steinman Aug. 7, 1951 2,611,718 Steinman Sept. 23, 1952 2,673,824 Beifeld et al Mar. 30, 1954 2,754,223 Caroselli July 10, 1956 2,757,160 Anderson July 31, 1956 2,851,379 Staudinger et al Sept. 9, 1958 2,891,885 Brooks June 23, 1959 2,931,739 Marzocchi et al Apr. 5, 1960 2,932,623 Glassen et a1 Apr. 12, 1960 2,937,230 Rogers May 17, 1960 2,938,812 Marzocchi et al May 31, 1960 2,951,772 Marzocchi .et al Sept. 6, 1960 2,951,782 Eilerman Sept. 6, 1960 FOREIGN PATENTS 543,092 Canada July 2, 1957 OTHER REFERENCES Polyesters and Their Applicants, Bjorksten Research Laboratories, Inc., Reinhold Publishing Corp., New York, 1956, lines 1626 and 30-33, page 11.
Claims (1)
1. GLASS FIBERS AND FABRICS FORMED THEREOF AND A SIZE ON THE GLASS FIBER SURFACES HAVING, AS AN ESSENTIAL INGREDIENT, THE REACTION PRODUCT OF AN IMIDAZOLINE HAVING A LONG CHAIN FATTY ACID GROUP IN WHICH THE LONG CHAIN FATTY ACID GROUP CONTAINS AT LEAST 5 CARBON ATOMS AND AN UNSATURATED POLYESTER RESIN FORMER IN AN UNCURED STAGE.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80260159 US3097963A (en) | 1959-03-30 | 1959-03-30 | Sized glass fibers and composition |
ES0256107A ES256107A1 (en) | 1959-03-30 | 1960-02-27 | Sized glass fibers and composition |
FR821812A FR1254072A (en) | 1959-03-30 | 1960-03-18 | Sizing composition for glass fibers and their fabrics |
CH327460A CH432737A (en) | 1959-03-30 | 1960-03-23 | Glass thread |
BE588954A BE588954A (en) | 1959-03-30 | 1960-03-23 | Sizing composition for glass fibers and their fabrics. |
CH602761A CH423654A (en) | 1959-03-30 | 1960-03-23 | Use of glass threads to make fabrics |
GB1051360A GB941374A (en) | 1959-03-30 | 1960-03-24 | Improvements in or relating to the sizing of glass fibres |
DEO7313A DE1191330B (en) | 1959-03-30 | 1960-03-28 | Process for the production of coatings on glass fibers and glass fiber fabrics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80260159 US3097963A (en) | 1959-03-30 | 1959-03-30 | Sized glass fibers and composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US3097963A true US3097963A (en) | 1963-07-16 |
Family
ID=25184183
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US80260159 Expired - Lifetime US3097963A (en) | 1959-03-30 | 1959-03-30 | Sized glass fibers and composition |
Country Status (7)
Country | Link |
---|---|
US (1) | US3097963A (en) |
BE (1) | BE588954A (en) |
CH (2) | CH423654A (en) |
DE (1) | DE1191330B (en) |
ES (1) | ES256107A1 (en) |
FR (1) | FR1254072A (en) |
GB (1) | GB941374A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3271182A (en) * | 1958-11-26 | 1966-09-06 | Chausson Usines Sa | Process for producing sheets of reinforced polyester resin |
US3376159A (en) * | 1964-07-28 | 1968-04-02 | Rohm & Haas | Treatment of siliceous fibers with aqueous mixtures of various unsaturated poly-imidazoline anchoring agents and resulting article |
US3414432A (en) * | 1965-10-04 | 1968-12-03 | Exxon Research Engineering Co | Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts |
US3441436A (en) * | 1966-02-09 | 1969-04-29 | American Cyanamid Co | Tool qualification film comprising a woven fabric coated with a resinous mixture for use in determining the effectiveness of tools |
US3920596A (en) * | 1973-06-27 | 1975-11-18 | Kao Corp | Sizing agent for glass fibers |
US3923708A (en) * | 1973-06-27 | 1975-12-02 | Kao Corp | Sizing agent for glass fibers |
US4009132A (en) * | 1974-12-24 | 1977-02-22 | Kao Soap Co., Ltd. | Sizing agent for glass fibers |
US4244844A (en) * | 1977-01-19 | 1981-01-13 | Saint-Gobain Industries | Aqueous size for glass fibers |
US5354829A (en) * | 1992-06-30 | 1994-10-11 | Ppg Industries, Inc. | Silylated polyamine polymers and a method of treating fibers |
US20050276960A1 (en) * | 2004-06-15 | 2005-12-15 | Lee Jerry H C | Fatty amide composition for wet use chopped strand glass fibers |
FR2898900A1 (en) * | 2006-03-24 | 2007-09-28 | Saint Gobain Vetrotex | Composition useful for the manufacture of lubricant mineral fibers comprises water and dry extract of coupling agent and polyvinylpyrrolidone |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2146210A (en) * | 1936-11-04 | 1939-02-07 | Du Pont | Synthetic resins |
US2468086A (en) * | 1948-06-21 | 1949-04-26 | Morton Chemical Co | Process of rendering anionic coating materials adherent to anionic bases |
US2544668A (en) * | 1946-04-27 | 1951-03-13 | Du Pont | Werner-type chromium compounds |
US2552910A (en) * | 1947-04-16 | 1951-05-15 | Owens Corning Fiberglass Corp | Coated glass fibers and method of making same |
US2563288A (en) * | 1945-11-13 | 1951-08-07 | Owens Corning Fiberglass Corp | Fibrous glass product and method of making the same |
US2563289A (en) * | 1947-06-12 | 1951-08-07 | Owens Corning Fiberglass Corp | Coated glass fibers and method for producing same |
US2611718A (en) * | 1947-03-14 | 1952-09-23 | Owens Corning Fiberglass Corp | Glass fibers coated with werner type complex and method of making same |
US2673824A (en) * | 1949-08-26 | 1954-03-30 | Owens Corning Fiberglass Corp | Process of producing vapor permeable fluid repellent fabrics |
US2754223A (en) * | 1952-01-24 | 1956-07-10 | Owens Corning Fiberglass Corp | Coated glass fiber and method of making |
US2757160A (en) * | 1953-03-04 | 1956-07-31 | Allied Chem & Dye Corp | Stable non-tacky granular filled unsaturated alkyd molding compound comprising a liquid monomer and a compatible polymer |
CA543092A (en) * | 1957-07-02 | P. Biefeld Lawrence | Treatment of mineral fibres | |
US2851379A (en) * | 1953-11-18 | 1958-09-09 | Distillers Co Yeast Ltd | Process of impregnating material with a resinous bonding composition |
US2891885A (en) * | 1953-11-16 | 1959-06-23 | Us Rubber Co | Method of making composite glasspolyester structures |
US2931739A (en) * | 1956-10-08 | 1960-04-05 | Owens Corning Fiberglass Corp | Plastics and laminates formed of glass fibers and epoxy resins |
US2932623A (en) * | 1956-04-02 | 1960-04-12 | Gen Mills Inc | Thixotropic coating vehicle containing a short oil alkyd resin and a copolymer polyamide resin |
US2937230A (en) * | 1954-05-28 | 1960-05-17 | Westinghouse Electric Corp | Resinous reaction products of unsaturated polyesters organopolysiloxanes, and unsaturated monomers and electrical members insulated therewith |
US2938812A (en) * | 1954-04-21 | 1960-05-31 | Owens Corning Fiberglass Corp | Treated glass fibers and compositions for use in same |
US2951772A (en) * | 1956-12-10 | 1960-09-06 | Owens Corning Fiberglass Corp | Treatments for fibrous glass used to reinforce resins |
US2951782A (en) * | 1956-01-03 | 1960-09-06 | Pittsburgh Plate Glass Co | Glass fiber treatment |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE535636A (en) * | 1954-02-11 | |||
GB790837A (en) * | 1954-04-24 | 1958-02-19 | British Paints Ltd | Improvements in or relating to the treatment of fibrous materials with resinous condensation products |
-
1959
- 1959-03-30 US US80260159 patent/US3097963A/en not_active Expired - Lifetime
-
1960
- 1960-02-27 ES ES0256107A patent/ES256107A1/en not_active Expired
- 1960-03-18 FR FR821812A patent/FR1254072A/en not_active Expired
- 1960-03-23 CH CH602761A patent/CH423654A/en unknown
- 1960-03-23 CH CH327460A patent/CH432737A/en unknown
- 1960-03-23 BE BE588954A patent/BE588954A/en unknown
- 1960-03-24 GB GB1051360A patent/GB941374A/en not_active Expired
- 1960-03-28 DE DEO7313A patent/DE1191330B/en active Pending
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA543092A (en) * | 1957-07-02 | P. Biefeld Lawrence | Treatment of mineral fibres | |
US2146210A (en) * | 1936-11-04 | 1939-02-07 | Du Pont | Synthetic resins |
US2563288A (en) * | 1945-11-13 | 1951-08-07 | Owens Corning Fiberglass Corp | Fibrous glass product and method of making the same |
US2544668A (en) * | 1946-04-27 | 1951-03-13 | Du Pont | Werner-type chromium compounds |
US2611718A (en) * | 1947-03-14 | 1952-09-23 | Owens Corning Fiberglass Corp | Glass fibers coated with werner type complex and method of making same |
US2552910A (en) * | 1947-04-16 | 1951-05-15 | Owens Corning Fiberglass Corp | Coated glass fibers and method of making same |
US2563289A (en) * | 1947-06-12 | 1951-08-07 | Owens Corning Fiberglass Corp | Coated glass fibers and method for producing same |
US2468086A (en) * | 1948-06-21 | 1949-04-26 | Morton Chemical Co | Process of rendering anionic coating materials adherent to anionic bases |
US2673824A (en) * | 1949-08-26 | 1954-03-30 | Owens Corning Fiberglass Corp | Process of producing vapor permeable fluid repellent fabrics |
US2754223A (en) * | 1952-01-24 | 1956-07-10 | Owens Corning Fiberglass Corp | Coated glass fiber and method of making |
US2757160A (en) * | 1953-03-04 | 1956-07-31 | Allied Chem & Dye Corp | Stable non-tacky granular filled unsaturated alkyd molding compound comprising a liquid monomer and a compatible polymer |
US2891885A (en) * | 1953-11-16 | 1959-06-23 | Us Rubber Co | Method of making composite glasspolyester structures |
US2851379A (en) * | 1953-11-18 | 1958-09-09 | Distillers Co Yeast Ltd | Process of impregnating material with a resinous bonding composition |
US2938812A (en) * | 1954-04-21 | 1960-05-31 | Owens Corning Fiberglass Corp | Treated glass fibers and compositions for use in same |
US2937230A (en) * | 1954-05-28 | 1960-05-17 | Westinghouse Electric Corp | Resinous reaction products of unsaturated polyesters organopolysiloxanes, and unsaturated monomers and electrical members insulated therewith |
US2951782A (en) * | 1956-01-03 | 1960-09-06 | Pittsburgh Plate Glass Co | Glass fiber treatment |
US2932623A (en) * | 1956-04-02 | 1960-04-12 | Gen Mills Inc | Thixotropic coating vehicle containing a short oil alkyd resin and a copolymer polyamide resin |
US2931739A (en) * | 1956-10-08 | 1960-04-05 | Owens Corning Fiberglass Corp | Plastics and laminates formed of glass fibers and epoxy resins |
US2951772A (en) * | 1956-12-10 | 1960-09-06 | Owens Corning Fiberglass Corp | Treatments for fibrous glass used to reinforce resins |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3271182A (en) * | 1958-11-26 | 1966-09-06 | Chausson Usines Sa | Process for producing sheets of reinforced polyester resin |
US3376159A (en) * | 1964-07-28 | 1968-04-02 | Rohm & Haas | Treatment of siliceous fibers with aqueous mixtures of various unsaturated poly-imidazoline anchoring agents and resulting article |
US3414432A (en) * | 1965-10-04 | 1968-12-03 | Exxon Research Engineering Co | Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts |
US3441436A (en) * | 1966-02-09 | 1969-04-29 | American Cyanamid Co | Tool qualification film comprising a woven fabric coated with a resinous mixture for use in determining the effectiveness of tools |
US3920596A (en) * | 1973-06-27 | 1975-11-18 | Kao Corp | Sizing agent for glass fibers |
US3923708A (en) * | 1973-06-27 | 1975-12-02 | Kao Corp | Sizing agent for glass fibers |
US4009132A (en) * | 1974-12-24 | 1977-02-22 | Kao Soap Co., Ltd. | Sizing agent for glass fibers |
US4244844A (en) * | 1977-01-19 | 1981-01-13 | Saint-Gobain Industries | Aqueous size for glass fibers |
US4246145A (en) * | 1977-01-19 | 1981-01-20 | Saint-Gobain Industries | Aqueous size for glass fibers |
US5354829A (en) * | 1992-06-30 | 1994-10-11 | Ppg Industries, Inc. | Silylated polyamine polymers and a method of treating fibers |
US20050276960A1 (en) * | 2004-06-15 | 2005-12-15 | Lee Jerry H C | Fatty amide composition for wet use chopped strand glass fibers |
FR2898900A1 (en) * | 2006-03-24 | 2007-09-28 | Saint Gobain Vetrotex | Composition useful for the manufacture of lubricant mineral fibers comprises water and dry extract of coupling agent and polyvinylpyrrolidone |
WO2007113425A1 (en) * | 2006-03-24 | 2007-10-11 | Ocv Intellectual Capital, Llc | Needled glass mat |
US20090220729A1 (en) * | 2006-03-24 | 2009-09-03 | Francois Roederer | Needle-Punched Glass Mat |
Also Published As
Publication number | Publication date |
---|---|
FR1254072A (en) | 1961-02-17 |
CH423654A (en) | 1966-10-31 |
BE588954A (en) | 1960-07-18 |
GB941374A (en) | 1963-11-13 |
ES256107A1 (en) | 1960-11-01 |
CH432737A (en) | 1967-09-15 |
CH327460A4 (en) | 1966-11-30 |
DE1191330B (en) | 1965-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2801189A (en) | Glass fiber article and process of plural coated fiber and process of preparation | |
US2931739A (en) | Plastics and laminates formed of glass fibers and epoxy resins | |
US5038555A (en) | Twistable chemically treated glass fibers, fabrics and coated articles | |
US3097963A (en) | Sized glass fibers and composition | |
EP0705861B1 (en) | Silylated polyamine polymer lubricants with and without other components, substrates treated with these polymers and method of treating the substrates | |
US4795678A (en) | Chemically treated glass fibers | |
CN1191523A (en) | Forming size compositions, glass fibres coated with same and fabrics woven from such coated fibres | |
US3207623A (en) | Sized glass fiber | |
TW472080B (en) | Sizing composition for glass yarns, process using this composition and products resulting therefrom | |
US2593818A (en) | Colored glass fiber product and method of producing the same | |
US3143405A (en) | Method of producing polyamide coated glass fibers | |
US5466528A (en) | Chemically treated glass type substrates with vinyl polymer compatibility | |
US3870547A (en) | Starch coated fibers for embedding in resin matrix forming materials and composites so formed | |
JPH07115893B2 (en) | Strands for fiberglass fabrics | |
US3066383A (en) | Finish for staple glass fibers and yarns manufactured thereof | |
US3042544A (en) | Yarns of staple glass fibers and compositions and methods for manufacturing same | |
US3025588A (en) | Glass fiber treatment | |
US2958114A (en) | Glass fiber yarns and compositions used in the manufacture of same | |
US4351752A (en) | Detackified aqueous sizing composition comprising liquid polymer and free radical generator | |
US4233809A (en) | Size composition for glass fibers | |
US4656084A (en) | Aqueous size composition with pH regulator | |
JPH09208268A (en) | Bundling agent for glass fiber and fabric of glass fiber | |
US3040413A (en) | Glass fiber yarns and compositions for use in the manufacture of same | |
EP0496195B1 (en) | Starch-oil treatment for glass fibers | |
JPS6018613B2 (en) | Bulkized glass fiber strand yarn processed product |